EP2821442B1 - Mousse de caoutchouc de silicone et de céramique et procédé pour le préparer - Google Patents

Mousse de caoutchouc de silicone et de céramique et procédé pour le préparer Download PDF

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Publication number
EP2821442B1
EP2821442B1 EP12827802.5A EP12827802A EP2821442B1 EP 2821442 B1 EP2821442 B1 EP 2821442B1 EP 12827802 A EP12827802 A EP 12827802A EP 2821442 B1 EP2821442 B1 EP 2821442B1
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Prior art keywords
ceramic
parts
rubber
silicone rubber
lump
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EP12827802.5A
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German (de)
English (en)
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EP2821442A4 (fr
EP2821442A1 (fr
Inventor
Shufeng Kang
Heping Zhou
Yuan Zhao
Weidong Liu
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Shenzhen Woer Heat Shrinkable Material Co Ltd
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Shenzhen Woer Heat Shrinkable Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers

Definitions

  • the present invention relates to a rubber foam, and particularly to a ceramic silicone rubber foam having a fire prevention function.
  • the magnesium oxide mineral fire-resistant insulating cable has the following disadvantages in manufacturing and application: first, high equipment costs; specialized production and processing equipment is required for the magnesium oxide mineral fire-resistant insulating cable, and the equipment cost is high; secondly, high production costs; the protective covering of the magnesium oxide mineral fire-resistant insulating cable is made of copper, and the price of copper is high, which leads to high production costs; as a result, the magnesium oxide mineral fire-resistant insulating cable is limited to a certain degree during actual application; thirdly, inconvenience during production and processing, transportation, line laying and installation, and use; the copper jacket magnesium oxide mineral fire-resistant insulating cable has special requirements in the process of production and processing, transportation, line laying and installation and use; for example, the production and processing of the magnesium oxide mineral fire-resistant insulating cable is not as convenient as that of high-molecule materials, the laying and installation is complex, and the costs of raw materials are high; therefore, the cable is not yet applied in a wide range, especially in civil buildings.
  • the mica tape wound fire-retardant cable needs to be wound by multiple layers of mica tape in the production process. Due to the restriction of technological conditions, lap defects always occur at the lap seam. In addition, the mica tape gets brittle and falls off easily after being burned, which greatly reduces the fire retardant effect, and results in a line short; therefore, it is difficult to ensure safe and smooth power supply and communication in the case of a fire.
  • a fire-resistant material is in urgent need to replace the magnesium oxide mineral fire-resistant insulating or mica tape winding manner, so as to achieve the fire resistant function.
  • An objective of the present application is to provide a ceramic silicone rubber foam that can be easily processed, has low production costs and has a fire resistant function, and a method for preparing the same and a use of the same.
  • a ceramic silicone rubber foam comprising, by weight:
  • the silicone rubber is one or more of dimethyl silicone rubber, methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber.
  • the viscosity of the silicone oil is 10 to 1,000 centipoises.
  • the coupling agent is any one or more of a silane coupling agent, a titanate coupling agent and an aluminium-titanium compound coupling agent.
  • the coupling agent is one or more of ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, triisostearoyl isopropoxy titanate and ethylene dioleoyltitanate.
  • the foaming agent is one or more of azodicarbonamide, dinitrosopentamethylene tetramine and 4,4'-oxybis(benzenesulfonyl hydrazide).
  • the foaming auxiliary agent is one or more of zinc stearate, calcium stearate and active zinc oxide.
  • a method for preparing a ceramic silicone rubber foam comprising:
  • a method for preparing a ceramic silicone rubber foam comprising:
  • a ceramic silicone rubber flame-retardant foam comprising the ceramic silicone rubber foam according to claim 1, 2, 3, 4 or 5, and further comprising 5 to 30 parts of a flame retardant.
  • the flame retardant is a halogen-free flame retardant.
  • the halogen-free flame retardant is one or more of red phosphorus, a phosphate flame retardant, magnesium hydroxide, aluminium hydroxide, zinc borate, ammonium polyphosphate, melamine pyrophosphate or polyphosphate and a pentaerythritol flame retardant.
  • the flame retardant is a halogen-containing flame retardant.
  • the halogen-containing flame retardant is one or more of chlorinated paraffin, tetrachlorophthalic anhydride, dibromobenzene ester, tetrabromoethane, decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol, octabromoether, brominated polystyrene and brominated epoxy resin.
  • a method for preparing a ceramic silicone rubber flame-retardant foam comprising:
  • the ceramic silicone rubber provided by the present application is a novel high-molecule composite material, which can be easily processed and has low production costs; the material is non-toxic and odourless at room temperature, and has good flexibility and elasticity in addition to properties of normal silicone rubbers; after being burned at a temperature of 650°C to 3,000°C for more than 3 min, the organic components in the silicone rubber may ablated and converted into a ceramic shell in a very short period of time rather than burned into ashes; moreover, the ceramic shell form a hard protective layer, and the protective layer isolates an article from the outside flame, thereby preventing the article from being continuously burnt by the flame and damaged. The longer the ablation time is, the higher the temperature is, and the harder the shell is.
  • the smoke generated by the ceramic silicone rubber of the present application in the early 2 to 3 min of the ablation is non-toxic and free of halogen, because the smoke is mainly generated by the combustion of organic silicon, and the smoke disappears after 2 to 3 min of combustion, and no smoke is generated any more in the process of blocking the flame. Therefore, the ceramic silicone rubber of the present application is an excellent fire resistant material.
  • the ceramic silicone rubber foam not only has the fire resistance function of the ceramic silicone rubber, but also has a low density and a light weight after foaming compared with the ceramic silicone rubber of an equal volume; the thermal insulation, heat preservation and sound insulation performances of the ceramic silicone rubber foam are improved; therefore, the ceramic silicone rubber foam may be used as a thermal insulating, heat preserving and sound insulating material.
  • the ceramic silicone rubber flame-retardant foam also has the flame retardant function, that is, due to the flame retardance, the ceramic silicone rubber flame-retardant foam may first remain nonflammable, so that the fire resistant and flame retardant performance is improved, and the first lien of defense against fire is formed; if the outside flame reaches a certain level and breaks through the first line of defense, the organic components in the silicone rubber may be ablated and converted into a ceramic shell in a very short period of time rather than burnt into ashes, and the ceramic shell forms a hard protective layer, and the protective layer isolates an article from the outside flame, thereby preventing the article from being continuously burnt by the flame and damaged and forming a second line of defense against fire.
  • the ceramic silicone rubber in this embodiment contains, by weight:
  • the first preparation method includes the following steps:
  • the ceramic silicone rubber in this embodiment is a novel high-molecule composite material; the ceramic silicone rubber is non-toxic and odourless at room temperature, and has good flexibility and elasticity in addition to properties of normal silicone rubbers; after being burned at a temperature of 650°C to 3,000°C for more than 3 min, the organic components in the silicone rubber may be ablated and converted into a ceramic shell in a very short period rather than burned into ashes; moreover, the ceramic shell form a hard protective layer, and the protective layer isolates an article from the outside flame, thereby preventing the article from being continuously burnt by the flame and damaged. The longer the ablation time is, the higher the temperature is, and the harder the shell is.
  • the smoke generated by the ceramic silicone rubber of the present application in the early 2 to 3 min of the ablation is non-toxic and free of halogen, because the smoke is mainly generated by the combustion of organic silicon, and the smoke disappears after 2 to 3 min of combustion, and no smoke is generated any more in the process of blocking the flame. It can be seen from the properties of the ceramic silicone rubber in the embodiments that, the ceramic silicone rubber in this embodiment is an excellent fire resistant material.
  • the ceramic silicone rubber in this embodiment Due to the excellent properties, the ceramic silicone rubber in this embodiment has wide applications and good application prospects.
  • a cross-linking agent may be a peroxide vulcanizing agent, such as 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (commonly known as DHBP), 2,4-dichlorobenzoyl chloride (commonly known as DCOC) and dicumyl peroxide (commonly known as DCP).
  • DHBP 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane
  • DCOC 2,4-dichlorobenzoyl chloride
  • DCP dicumyl peroxide
  • the cable prepared according to the method is subjected to an SGS test, and the test results are consistent with the requirements of the EU RoHS instruction 2002/95/EC and subsequent amendments; the results of smoke toxicity test by the National Fire Protection Building Materials Quality Supervision and Inspection Center show that, according to GB/T 20285-2006, the smoke toxicity of the material is determined to reach a quasi-security level 1 (ZA1); the results of 90 min-fire test, the material is in accordance with GB/T 19666-2005.
  • ZA1 quasi-security level 1
  • Example 1 60 parts of dimethylsilicone rubber (MQ), 20 parts of silicon dioxide, 1 part of methyl silicone oil, 0.1 part of KH560, 20 parts of silicate glass powder and 1 part of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane were used to prepare a ceramic silicone rubber according to the first method for preparing a ceramic silicone rubber, and when the ceramic silicone rubber is vulcanized and formed, 1 part of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane was added.
  • MQ dimethylsilicone rubber
  • Example 2 100 parts of methyl phenyl vinyl silicone rubber (PVMQ), 100 parts of silicon dioxide, 20 parts of hydroxyl silicone oil, 10 parts of OL-T671, 120 parts of borate glass powder and 5 parts of dicumyl peroxide (commonly known as DCP) were used to prepare a ceramic silicone rubber according to the second method for preparing a ceramic silicone rubber, and when the ceramic silicone rubber is vulcanized and formed, 5 parts of dicumyl peroxide was added.
  • PVMQ methyl phenyl vinyl silicone rubber
  • DCP dicumyl peroxide
  • Example 3 30 parts of dimethylsilicone rubber (MQ), 50 parts of methyl vinyl silicone rubber (VMQ), 80 parts of silicon dioxide, 10 parts of hydroxyl silicone oil, 3 parts of A172, 70 parts of phosphate glass powder and 3 parts of 2,4-dichlorobenzoyl chloride (commonly known as DCOC) were used to prepare a ceramic silicone rubber according to the second method for preparing a ceramic silicone rubber, and when the ceramic silicone rubber is vulcanized and formed, 3 parts of 2,4- dichlorobenzoyl chloride was added.
  • DCOC 2,4-dichlorobenzoyl chloride
  • the ceramic silicone rubber in this embodiment may further contains (6) 10 to 35 parts of a foaming agent; (7) 1 to 10 parts of a foaming auxiliary agent, so as to form a ceramic silicone rubber foam.
  • the foaming agent is one or more of azodicarbonamide (AC), dinitrosopentamethylene tetramine (foaming agent H) and 4,4'-oxybis(benzenesulfonyl hydrazide).
  • the foaming auxiliary agent is one or more of zinc stearate, calcium stearate and active zinc oxide.
  • the method for preparing the ceramic silicone rubber foam is similar to the method for preparing the ceramic silicone rubber, and includes two preparation methods, where the first preparation method includes the following steps:
  • the second method for preparing the ceramic silicone rubber foam is as follows:
  • Example 4 70 parts of dimethylsilicone rubber (MQ), 50 parts of silicon dioxide, 6 parts of methyl silicone oil, 2 parts of A171, 30 parts of silicate glass powder, 1 part of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (commonly known as DHBP), 10 parts of azodicarbonamide (AC), 2 parts of zinc stearate were used to prepare a ceramic silicone rubber foam according to the first method for preparing a ceramic silicone rubber foam, and when the ceramic silicone rubber foam is vulcanized and formed, 1 part of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane was added.
  • MQ dimethylsilicone rubber
  • silicon dioxide silicon dioxide
  • 6 parts of methyl silicone oil 2 parts of A171, 30 parts of silicate glass powder
  • 1 part of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane commonly known as DHBP
  • AC azodicarbonamide
  • Example 5 90 parts of methyl phenyl vinyl silicone rubber (PVMQ), 95 parts of silicon dioxide, 20 parts of hydroxyl silicone oil, 3 parts of A172, 5 parts of KR-TTS, 115 parts of borate glass powder, 35 parts of dinitrosopentamethylene tetramine (a foaming agent H), and 9 parts of active zinc oxide were used to prepare a ceramic silicone rubber foam according to the second method for preparing a ceramic silicone rubber foam, and when the ceramic silicone rubber foam is vulcanized and formed, 5 parts of dicumyl peroxide was added.
  • PVMQ methyl phenyl vinyl silicone rubber
  • Example 6 80 parts of methyl vinyl silicone rubber (VMQ), 80 parts of silicon dioxide, 10 parts of hydroxyl silicone oil, 3 parts of A172, 70 parts of phosphate glass powder, 3 parts of 2,4-dichlorobenzoyl chloride (commonly known as DCOC), 11 parts of azodicarbonamide (AC), 22 parts of 4,4'-oxybis(benzenesulfonyl hydrazide), 2 parts of zinc stearate and 5 parts of calcium stearate were used to prepare a ceramic silicone rubber foam according to the second method for preparing a ceramic silicone rubber foam, and when the ceramic silicone rubber foam is vulcanized and formed, 3 parts of 2,4-dichlorobenzoyl chloride was added.
  • DCOC 2,4-dichlorobenzoyl chloride
  • AC azodicarbonamide
  • AC 4,4'-oxybis(benzenesulfonyl hydrazide)
  • 2 parts of zinc stearate and 5 parts of calcium stearate were used
  • the ceramic silicone rubber foam not only has the fire resistance function of the ceramic silicone rubber, but also has the advantages of low density and light weight after foaming compared with the ceramic silicone rubber of an equal volume; the thermal insulation, heat preservation and sound insulation performances of the ceramic silicone rubber foam are also improved; therefore, the ceramic silicone rubber foam may be used as a thermal insulating, heat preserving and sound insulating material.
  • the ceramic silicone rubber in this embodiment can not only form a ceramic silicone rubber foam, and further contains, on the basis of the ceramic silicone rubber foam: (8) 5 to 30 parts of a flame retardant, so as to form a ceramic silicone rubber flame-retardant foam.
  • the flame retardant can be a halogen-free flame retardant or a halogen-containing flame retardant.
  • the halogen-free flame retardant may be one or more of red phosphorus, a phosphate flame retardant, magnesium hydroxide, aluminium hydroxide, zinc borate, ammonium polyphosphate, melamine polyphosphate or polyphosphate and a pentaerythritol flame retardant.
  • the halogen-containing flame retardant is one or more of chlorinated paraffin, tetrachlorophthalic anhydride, dibromobenzene ester, tetrabromoethane, decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol, octabromoether, brominated polystyrene and brominated epoxy resin.
  • the method for preparing the ceramic silicone rubber flame-retardant foam is similar to the method for preparing the ceramic silicone rubber foam, and includes two preparation methods, where the first preparation method is as follows:
  • the second method for preparing the ceramic silicone rubber foam is as follows:
  • Example 7 80 parts of dimethylsilicone rubber (MQ), 10 parts of silicon dioxide, 3 parts of methyl silicone oil, 0.5 part of KH560, 20 parts of silicate glass powder, 1 part of dicumyl peroxide, 12 parts of azodicarbonamide (AC), 1 part of zinc stearate, 4 parts of red phosphorus were used to prepare a ceramic silicone rubber foam according to the first method for preparing a ceramic silicone rubber foam, and when the ceramic silicone rubber foam is vulcanized and formed, 1 part of dicumyl peroxide was added.
  • MQ dimethylsilicone rubber
  • 10 parts of silicon dioxide 10 parts of silicon dioxide, 3 parts of methyl silicone oil, 0.5 part of KH560, 20 parts of silicate glass powder, 1 part of dicumyl peroxide, 12 parts of azodicarbonamide (AC), 1 part of zinc stearate, 4 parts of red phosphorus were used to prepare a ceramic silicone rubber foam according to the first method for preparing a ceramic silicone rubber foam, and when the ceramic
  • Example 8 100 parts of methyl phenyl vinyl silicone rubber (PVMQ), 100 parts of silicon dioxide, 20 parts of hydroxyl silicone oil, 4 parts of KR-TTS, 120 parts of silicate glass powder, 5 parts of dicumyl peroxide, 35 parts of dinitrosopentamethylene tetramine (foaming agent H), 9 parts of active zinc oxide and 28 parts of aluminium hydroxide flame retardant were used to prepare a ceramic silicone rubber foam according to the second method for preparing a ceramic silicone rubber foam, and when the ceramic silicone rubber foam is vulcanized and formed, 5 parts of dicumyl peroxide was added.
  • PVMQ methyl phenyl vinyl silicone rubber
  • silicon dioxide 100 parts of silicon dioxide
  • 20 parts of hydroxyl silicone oil 20 parts of hydroxyl silicone oil
  • 4 parts of KR-TTS 120 parts of silicate glass powder
  • 5 parts of dicumyl peroxide 35 parts of dinitrosopentamethylene tetramine (foaming agent H)
  • Example 9 80 parts of methyl vinyl silicone rubber (VMQ), 80 parts of silicon dioxide, 10 parts of hydroxyl silicone oil, 3 parts of A171, 70 parts of phosphate glass powder, 3 parts of 2,4-dichlorobenzoyl chloride, 11 parts of azodicarbonamide (AC), 22 parts of 4,4'-oxybis(benzenesulfonyl hydrazide), 2 parts of zinc stearate, 6 parts of calcium stearate, 2 parts of ammonium polyphosphate and 14 parts of pentaerythritol flame retardant were used to prepare a ceramic silicone rubber foam according to the second method for preparing a ceramic silicone rubber foam, and when the ceramic silicone rubber foam is vulcanized and formed, 3 parts of 2,4-dichlorobenzoyl chloride was added.
  • the ceramic silicone rubber flame-retardant foam also has the flame retardant function, that is, due to the flame retardance, the ceramic silicone rubber flame-retardant foam first remains nonflammable, so that the fire resistant and flame retardant performance is improved, and the first lien of defense against fire is formed; if the outside flame reaches a certain level and breaks through the first line of defense, the organic components in the silicone rubber may be ablated and converted into a ceramic shell in a very short period of time rather than not be burnt into ashes, and the ceramic shell forms a hard protective layer, and the protective layer isolates an article from the outside flame, thereby preventing the article from being continuously burnt by the flame and damaged and forming a second line of defense against fire.
  • the ceramic silicone rubber of the present application is a novel high-molecule composite material, which can be easily processed and has low production costs; the material is non-toxic and odourless at room temperature, and has good flexibility and elasticity in addition to properties of normal silicone rubbers; after being burned at a temperature of 950°C for 90 min, the organic components in the silicone rubber may be ablated and converted into a ceramic shell in a very short period of time rather than burned into ashes; moreover, the ceramic shell form a hard protective layer, and the protective layer isolates an article from the outside flame, thereby preventing the article from being continuously burnt by the flame and damaged.
  • the smoke generated by the ceramic silicone rubber of the present application in the early 2 to 3 min of the ablation is non-toxic and free of halogen, because the smoke is mainly generated by the combustion of organic silicon, and the smoke disappears after 2 to 3 min of combustion, and no smoke is generated any more in the process of blocking the flame. Therefore, the ceramic silicone rubber of the present application is an excellent fire resistant material.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Claims (15)

  1. Mousse de caoutchouc de silicone et de céramique comprenant, en poids :
    60 à 100 parties de caoutchouc de silicone ;
    20 à 100 parties de dioxyde de silicium ;
    1 à 20 parties d'huile de silicone ;
    0,1 à 10 parties d'un agent de couplage ;
    20 à 120 parties d'une poudre de céramique, laquelle poudre de céramique est une ou plusieurs parmi une poudre de verre de silice, une poudre de verre de borate, une poudre de verre de phosphate et une poudre de verre au plomb ;
    10 à 35 parties d'un agent moussant ; et
    1 à 10 parties d'un agent auxiliaire de moussage.
  2. Mousse de caoutchouc de silicone et de céramique selon la revendication 1, dans laquelle le caoutchouc de silicone est un ou plusieurs parmi un caoutchouc de diméthylsilicone, un caoutchouc de méthylvinylsilicone et un caoutchouc de méthylphénylvinylsilicone.
  3. Mousse de caoutchouc de silicone et de céramique selon la revendication 1, dans laquelle la viscosité de l'huile de silicone est de 10 à 1000 centipoises.
  4. Mousse de caoutchouc de silicone et de céramique selon la revendication 1, dans laquelle l'agent de couplage est l'un quelconque ou plusieurs parmi un agent de couplage de type silane, un agent de couplage de type titanate et un agent de couplage de type composé d'aluminium et de titane.
  5. Mousse de caoutchouc de silicone et de céramique selon la revendication 1, dans laquelle l'agent de couplage est un ou plusieurs parmi le γ-(2,3-époxγ-propoxy)propyltriméthoxysilane, le vinyltriméthoxysilane, le vinyltris(β-méthoxyéthoxy)silane, l'isopropoxytitanate de triisostéaroyle et le dioléoyltitanate d'éthylène.
  6. Mousse de caoutchouc de silicone et de céramique selon la revendication 1, dans laquelle l'agent moussant est un ou plusieurs parmi l'azodicarbonamide, la dinitrosopentaméthylènetétramine et le 4,4'-oxybis-(benzènesulfonylhydrazide).
  7. Mousse de caoutchouc de silicone et de céramique selon la revendication 1, dans laquelle l'agent auxiliaire de moussage est un ou plusieurs parmi le stéarate de zinc, le stéarate de calcium et l'oxyde de zinc actif.
  8. Procédé pour préparer une mousse de caoutchouc de silicone et de céramique, comprenant :
    (1) le mélange de matériaux consistant en 60 à 100 parties de caoutchouc de silicone, 20 à 100 parties de dioxyde de silicium, 1 à 20 parties d'huile de silicone, 0,1 à 10 parties d'un agent de couplage, 10 à 35 parties d'un agent moussant, et 1 à 10 parties d'un agent auxiliaire de moussage, dans une machine de malaxage dans laquelle la température ne dépasse pas 100°C ;
    (2) la mise sous vide de la machine de malaxage pendant 30 à 120 minutes, la température étant maintenue non supérieure à 165°C ;
    (3) après mise sous vide de la machine de malaxage, l'addition de 20 à 120 parties de poudre de céramique dans la machine de malaxage, de façon que la poudre de céramique soit mélangée uniformément avec le mélange de caoutchouc de silicone, de dioxyde de silicium, d'huile de silicone, et d'un agent de couplage, de façon à former un caoutchouc de céramique analogue à une motte, la poudre de céramique étant une ou plusieurs parmi une poudre de verre de silicate, une poudre de verre de borate, une poudre de verre de phosphate et une poudre de verre au plomb ;
    (4) la sortie du caoutchouc de céramique analogue à une motte hors de la machine de malaxage, et le refroidissement du caoutchouc de céramique analogue à une motte ;
    (5) le broyage dans un malaxeur à cylindres du caoutchouc de céramique analogue à une motte refroidi, de façon à découper en feuilles le caoutchouc de céramique analogue à une motte ; et
    (6) la filtration du caoutchouc de céramique analogue à une feuille en bandes sur un filtre de caoutchouc, de façon que soit obtenue la mousse de caoutchouc de silicone et de céramique.
  9. Procédé pour préparer une mousse de caoutchouc de silicone et de céramique, comprenant :
    (1) le mélange de matériaux consistant en 60 à 100 parties de caoutchouc de silicone, 20 à 100 parties de dioxyde de silicium, 1 à 20 parties d'huile de silicone, 0,1 à 10 parties d'un agent de couplage, 20 à 120 parties d'une poudre de céramique, 10 à 35 parties d'un agent moussant, et 1 à 10 parties d'un agent auxiliaire de moussage, dans une machine de malaxage dans laquelle la température ne dépasse pas 100°C, la poudre de céramique étant une ou plusieurs parmi une poudre de verre de silicate, une poudre de verre de borate, une poudre de verre de phosphate et une poudre de verre au plomb ;
    (2) la mise sous vide de la machine de malaxage pendant 30 à 120 minutes, la température étant maintenue non supérieure à 165°C, et le mélange uniforme des matériaux pour former un caoutchouc de céramique analogue à une motte ;
    (3) la sortie du caoutchouc de céramique analogue à une motte hors de la machine de malaxage, et le refroidissement du caoutchouc de céramique analogue à une motte ;
    (4) le broyage dans un malaxeur à cylindres du caoutchouc de céramique analogue à une motte refroidi, de façon à découper en feuilles le caoutchouc de céramique analogue à une motte ; et
    (5) la filtration du caoutchouc de céramique analogue à une feuille en bandes sur un filtre de caoutchouc, de façon que soit obtenue la mousse de caoutchouc de silicone et de céramique.
  10. Mousse ignifugeante de caoutchouc de silicone et de céramique, comprenant la mousse de caoutchouc de silicone et de céramique selon la revendication 1, 2, 3, 4 ou 5, et comprenant en outre 5 à 30 parties d'un agent ignifugeant.
  11. Mousse ignifugeante de caoutchouc de silicone et de céramique selon la revendication 10, dans laquelle l'agent ignifugeant est un agent ignifugeant sans halogène.
  12. Mousse ignifugeante de caoutchouc de silicone et de céramique selon la revendication 11, dans laquelle l'agent ignifugeant sans halogène est un ou plusieurs parmi le phosphore rouge, un agent ignifugeant de type phosphate, l'hydroxyde de magnésium, l'hydroxyde d'aluminium, le borate de zinc, le polyphosphate d'ammonium, le pyrophosphate ou polyphosphate de mélamine, et un agent ignifugeant de type pentaérythritol.
  13. Mousse ignifugeante de caoutchouc de silicone et de céramique selon la revendication 10, dans laquelle l'agent ignifugeant est un agent ignifugeant contenant un halogène.
  14. Mousse ignifugeante de caoutchouc de silicone et de céramique selon la revendication 13, dans laquelle l'agent ignifugeant contenant un halogène est un ou plusieurs parmi la paraffine chlorée, l'anhydride tétrachlorophtalique, un ester de dibromobenzène, le tétrabromoéthane, le décabromodiphényléther, le décabromodiphényléthane, le tétrabromobisphénol, l'octabromoéther, le polystyrène bromé et une résine époxy bromée.
  15. Procédé pour préparer une mousse ignifugeante de caoutchouc de silicone et de céramique, comprenant :
    (1) le mélange de matériaux consistant en 60 à 100 parties de caoutchouc de silicone, 20 à 100 parties de dioxyde de silicium, 1 à 20 parties d'huile de silicone, 0,1 à 10 parties d'un agent de couplage, 20 à 120 parties d'une poudre de céramique, 10 à 35 parties d'un agent moussant, et 1 à 10 parties d'un agent auxiliaire de moussage, ainsi que 5 à 30 parties d'un agent ignifugeant, dans une machine de malaxage dans laquelle la température ne dépasse pas 100°C, la poudre de céramique étant une ou plusieurs parmi une poudre de verre de silicate, une poudre de verre de borate, une poudre de verre de phosphate et une poudre de verre au plomb ;
    (2) la mise sous vide de la machine de malaxage pendant 30 à 120 minutes, la température étant maintenue non supérieure à 165°C, et le mélange uniforme des matériaux pour former un caoutchouc de céramique analogue à une motte ;
    (3) la sortie du caoutchouc de céramique analogue à une motte hors de la machine de malaxage, et le refroidissement du caoutchouc de céramique analogue à une motte ;
    (4) le broyage dans un malaxeur à cylindres du caoutchouc de céramique analogue à une motte refroidi, de façon à découper en feuilles le caoutchouc de céramique analogue à une motte ; et
    (5) la filtration du caoutchouc de céramique analogue à une feuille en bandes sur un filtre de caoutchouc, de façon que soit obtenue la mousse ignifugeante de caoutchouc de silicone et de céramique.
EP12827802.5A 2011-08-29 2012-04-26 Mousse de caoutchouc de silicone et de céramique et procédé pour le préparer Active EP2821442B1 (fr)

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